The document describes improvements to the "oxo process" for producing oxygenated organic compounds from olefins using carbon monoxide, hydrogen, and a carbonylation catalyst. Specifically, it involves using a catalyst combination that is particularly effective for catalyzing the reaction. The oxo process typically involves three stages - an initial reaction of the olefin with carbon monoxide and hydrogen over a cobalt catalyst to produce aldehydes, removal of soluble metal compounds from the product, and then hydrogenation of the aldehydes to alcohols. The invention relates to improving the catalyst used in the first stage of the reaction.

1. * GB784628 (A)
Description: GB784628 (A) ? 1957-10-09
Improvements in the production of conjugated-unsaturated aldehydo carboxylic
acid esters
Description of GB784628 (A)
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The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
COMPLET SPECIFICATION
Improvements in the Production of Conjugated-Unsaturated
Aldehydo Carboxylic Acid Esters
We ; BADISCHE ANILIN- & SODA-FABRIK AKTIENGESELLSCHAFT, a Joint Stock
Com- pany organised under the aaws of Germany, of Ludwigshafen on
Rhein, Germany, do hereby declare the invention, for which we pray
that a payant may be granted to us, and the method by which it is to
be performed, to be particularly described in and by the following
statement :-
This invention relates to a process for the production of valable
conjugated-unsatur- ated aldehydo carboxylic acid esters, especially
of 4-methylhexadtene :- (2. 4)-al- (l)- oic acid-(6) and
2.6-dimethyloctatricne (2.4.6)-al-(1)-oic acid-(8) lower alkyl esters.
We hav efound that conjugated-unsaturated aldehydo carboxylic acid
esters are obtained by reacting, while excluding water, aldehydo
carboxylic acid esters of the general formula
<img class="EMIRef" id="026415699-00010001" />
in which m ! and n lare 0 or 1 or 2 and the sum of m and n is 1, 2 or
3, R represents hydrogen or a lower alkyl group and RI represents a
lower alkyl group, or the lower dialkyl acetals of said aldehydo
carboxylic acid esters, the terms lower alkyl meaning alkyls of from 1

2. to 4 carbon atoms, in the presence of acid condensing agents with a
vinyl ether of the general formula
R-CH = CH-OR1 in which R and R1 have the same meaning as above, R and
RI of the said general formulas being individually or cojointly either
the same or different radicals of the aforesaid kind, and heating the
resultant alkoxy aldehyde carboxylic acid esters or their dialkyl
acetals in the presence of at least 1 mol of water per 1 mol of alkoxy
aldehydo carboxylic acid ester with an acid until no more.'alcohol is
split off.
In the heating and splitting off of the alcohol more than 1 mol of
water per mol of alkcxy aldehydo carboxylic acid ester or its diallyl-
acetal can also be present. Often it is even advantageous to use an
excess of water, e. g.
10 mols. The water is preferably added in small portions during the
heating, advantage- ously in the presence of benzene or toluene.
Suitable initial aldehydo carboxylic acid esters are, for lexampls
2-or 4-methylbutene- (2)-al-(l)-oic acid-(4) methyl, ethyl or butyl
esters or their dimethyl or diethyl acetals, 1. 1.
3-trimethoxy-or-triethoxy-4-merhyl- hexene-(4)-oic acid-(6) mlethyl or
ethyl esters or 1. 1. 3-triethoxyhexene-(4)-oic acid- (6) ethyl ester.
Suitable vinyl ethers are, for example, vinyl or propenyl methyl,
ethyl ! or propyl ethers.
As acid condensing agents, there may be used for example, hydrogen
halides, such as hydrogen fluoride, chloride and bromide, boron
trifluoride, benzene, sulphonic acid p-toluene sulphonic acid or zinc
chloride. They can be used in an amount of from about 0. 05 to about
10%. with reference to ithe amount of reactants. The saint acid agents
may be used in the last step of the process, ive. in the splitting off
of alcool.
In the case of using the diethyl acetal of 2-methylbutene- (2)-al-
(l)-oic acid- (4) ethyl ester (I) and vinyl ethyl iether (II) as
starting materials, the process may be formulated as follows :
<img class="EMIRef" id="026415699-00020001" />
If the ester III and propenyl ethyl ether (V) are used as the starting
materials, the process may be formulated as follows : t
<img class="EMIRef" id="026415699-00020002" />
In this way for example the hitherto unknown 4-methyl-hexadiene-(2.4)
- al - (1)-oic acid-(6) ethyl ester IV is obtained by way of the
singly unsaturated monoethoxy diethylacetal carboxylic acid ester III
and the 2. 6dimethyloctatriene-(2. 4. 6)-al- (l)-oic. add- (S)- ethyl
ester VII by way of the singly unsaturated diethoxy diethylacetal
carboxylic acid ester VI.
The conjugated unsaturated aldehydo carboxylic acid esters obtainable
by the present process starting from technically accessible materials

3. are valuable intermediates for the synthesis of vitamins and
vitamin-like compounds.
The following Examples will further illustrate the invention but the
invention is not restricted to these Examples. The parts, are by
weight.
EXAMPLE 1.
100 parts of 2-methyl-butene- (2)-al- (l)- oic acid-(4) ethyl ester of
the boiling point 79 to 81 C. at 11 torr (obtainable by oxidation of
omega-hydroxy-beta-methyl-crotonic acid ethyl ester or by condensation
of propion- aldehyde with glyoxylic acid ethyl ester) are acetalized
by stirring with 110 parts of absolute alcohol, 3 parts of ammonium
nitrate and 180 parts of orthoformic acid ethyl ester for 15 hours at
room temperature and then for 10 minutes at 70'C. The 1.
l-diethoxy-2-methylbutene- (2)-oic acid- (4) ethyl ester thus
obatained in a yield of 206 parts boils at 88 to 91 C. at 0. 7 torr.
To 205 parts of this acetal ester there are added 0. 25 part of boron
fluoride etherate and then, at 40 to 45 C., 40 parts of vinyl ethyl
ether while stirring. After neutralization with potassium carbonate,
the whole is fractionally distilled; 90 parts of initial material
first pass over and then 130 parts of
1.1.3triethexy-4-methylhexene-(4)-oic acid- (6) ethyl ester of the
boiling point 110'to 113-
C. at 0. 4 torr are obtained.
20 parts of this ester are heated with 600 parts of benzene, 5 parts
of water and 0. 2 part of pttoluene sulphonic acid ssith continuous
reflux of the benzene until a transition temperature of 80'C., the
boiling point cf pure benzene, has been reached. The remaining benzene
solution is washed with 2 ,. potassium carbonate solution and then
with water, dried over sodium sulphate and the benzene evaporated.
There are obtained 18 pars of 4-methyl-hexadiene-(2.4)-al-(1)-oic acid
(6) ethyl ester melting at 57 C. (recrystallized from cyclohexane)
which in methanol solution exhibits an absorption spectrum having a
band with #max=272 millimicrons, e=27000. The corresponding n-butyl
ester prepared in an analogous manner has the boiling point 88 to 91
C. under a pressure of 0. 001 torr.
EXAMPLE 2.
To 128 parts of 1. 1. 3-triethoxy-4-methylhexene- (4)-oic acid-(6) ;
ethyl ester obtained, as described in the second paragraph of Example
1 there are added 0. 8 part of boron fluoride etherate and then, at 50
to 55 C., 35 parts of propenyl ethyl ether. Fractional distillation
yields 91 parts of initial materiaL and 34 parts of 1. 1. 3.
5-tetraethoxy-2. 6-dimethyloctene (6)-oic acid- (8) : ethyl ester of
the boiling point 160 to 165 C. at 0. 05 torr.
34 parts of this compound are heated with 600 parts of benzene, 5

4. parts of water and 0. 2 part of para-toluene sulphonic acid with
continuous return of the benzene until a transition temperature of
80'C., the boiling point of pure benzene, has been reached. The
remaining benzene solution is shaken with 2% potassium carbonate
solution and then with water, dried over sodium sulphate and the
solvent evaporated. The residue is distilled at a pressure of 0. 003
torr and a bath Item- perature of 120 C.
The 2. 6-dimzethyl-actariene-2. 4. 6)-al-(1)oic acid-(8) ethyl ester
thus obtained solidifies and upon recrystallization from cyclohexane
gives yellowish needles m & lting at 78 C.
When taken up in methanol its absorption spectrum shows the following
bandes-.' 300 millimicrons (inflection), e=29000 ; 315 millimicrons, #
= 48000 ; and 327 millimicrons, e = 40000.
EXEMPLE 3.
To a solution of 250 parts of 4-methylhexadiene-(2.4)-al-(1)-oic
acid-(6) ethyl ester (obtained by the method described in Example
1) in 230 parts of orthformic acid ethyl ester there is added a warm
solution of 1. 4 parts of ammonium nitrate in 140 parts of absolute
ethanol. After boiling for 1 hour under reflux, the dark coloured
solution is diluted with methylene chloride and washed with dilute
sodium carbonate solution. After drying over sodium sulphate, th
esolvent and excess ethyl orthofonn, ate are distilled off. In the
subse- quent fractional distillation in high vacuum, 300 parts of 1.
1-diethoxy-4-methyl-hexadiene (2. 4)-oic acid-(6) ethyl ester of the
boiling point 97 to 98 C. at 0. 05 torr pass over.
To this there are added 0. 4 part of boron trifluoride diemereate and,
gradually at 50 to 55 C., 100 parts of propenyl ethyl ether.
Care is faken by temporary cooling that the said temperature is not
exceeded. When all has been added, the whole is stirred for 30
minutes, cooled and neutralized with dibutyamine. The 1. 1.
3-triethoxy-2. 6-dimethyl-octa- diene- (4. 6)-oic acid- (8) ethyl
ester thus obtained boils at 126 to 128 C at. 0. 01 torr ; the yield
is 330 parts. This triethoxy carboxylic acid ester is heated in
toluene solution with small amounts of water with the addition of
para-toluene sulphonic acid until a transition temperature of 111 C,
the boiling point of pure toluene, has been reached and it is further
treated as described in the second paragraph of Example 2. 180 parts
of 2.6-dimethyl-octatriene-(2.4.6)-al-(1) - oic acid (8) ethyl ester
of the melting point 78 C. are thus obtained.
EXAMPLE 4.
To 200 parts of 2-methyl-butene- (2)-al- (l)- oic acid-(4) lethyR
ester thlere are added 0. 4 part of boron trifluoride dietherate and
then, at 45 C, 60 pars of vinyl ethyl ether. The neutralized rection
product is dissolved in 300 parts of toluene and treated with small

5. amounts of water and para-itoluene sulphonic acid and heated as
described in the last paragraph of Example 1 until the boiling point
of pure toluene has been reached. The solvent is distilled off and the
residue fractionally distilled in vacuo, whereby there pass over 120
parts of unchanged initial material and 60 parts of
4-methyl-hexadiene-(2.4)-al-(1)-oic acid-(6) ethyl ester of the
boiling point 87 to 89 C. at 0.07 torr, which immediately crystallizes
and melts zat 57 C. after being once recrystallized from cyclohexane.
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* 5.8.23.4; 93p
* GB784629 (A)
Description: GB784629 (A) ? 1957-10-09
Improved oxo process
Description of GB784629 (A)
COMPLETE SPECIFICATION
Improved Oxo Process WeSSO RESEARCHAND ENGINEERING
COMPANY, a Corporation duly organised and existing underthelawis of
the state of Delaware, United States of America, of Elizabeth,
New Jersey, United States of America, do hereby declare the invention,
for which we pray that a patent may be granted to us, and the method
by which it is to be performed, to be particularly described in and by
the following statement :-
The present anvention relates to the prepara- tion, of oxygenated
organic compounds by the reaction of carbon monoxide and hydrogen with
carbon compounds containing olefinic linkages in the presence of a
carbonylation catalyst. More specifically the present invention
relates to catalyst combinations particularly adapted to catalyze this
reaction.

6. It is now well known in the art that oxy- genated organic compounds
may be synthe- sized from organic compounds containing olefinic
linkages by a reaction with carbon monoxide and hydrogen in the
presence of a catalyst containing metals of the iron group,
particularly cobalt, in an essentiallythree-stage process. In the
first stage, the olefinic material, catalyst and the proper
proportions of CO and
H2 are reacted to give a product consisting predominantly of aldehydes
containing one more carbon atom than the reacted olefin.
This oxygenated organic mixture, which contains dissolve in it salts
and the carbonyls and molecular complexes of the metal catalyst, is
treated in a second stage to cause removal of soluble metal compounds
from the organic material in a catalyst removal zone. The
catalyst-free material is then generally hydrogenated tothe
corresponding alcohols, or may be oxidized to the corresponding acid.
This carbonylation reaction provides a particularly attractive method
for preparing valable primary alcohols which find large markets,
particularly as intermediates for plasticizers, detergents and
solvents. Amenable to the reaction are long and short chained olefinic
compounds, depending upon the type of alcohol desired. Not only
(devins, but most organic compounds possessing at least one
nonaromatic carbon-carbon double bond may be reacted by this method.
Thus, straight and branch-chained olefins and diolefins, such as
propylene, butylene, pentene, hexene, heptene, butadiene, pentadiene,
styrene, olefin pcly- mers, such as di-and tri-isobutylene and hexene
and heptene dimers, polypropylene, olefinic fractions from the
hydrocarbon synthesis process, thermal or catalytic cracking
operations, and other sources of hydrocarbon fractions containing
olefins may be used as starting material, depending upon the nature of
the final product desired.
The catalyst in the first stage of the prior art processes is usually
added in the form of salts of the catalytically active metal with high
molecular fatty acids, such as stearic, oleic, palmitic and naphthenic
acids. Thus, suitable catalysts are, for example, cabalt oleate or
naphthenate. These salts are soluble in the liquid olefin feed and may
be supplied to the first stage as hydrocarbon solution or dissolved in
the olefin feed.
The synthesis gas mixture fed to the first stage may consist of any
ratio of H2 to CO, but preferably these gases are present in about
equal volumes. The conditions for reacting devis with H2 and CO vary
somewhat in accordance with the nature of the olefin feed, but the
reaction is generally conducted at pressures in the range of about
1500 to 4500 p.s.i.g., and at temperatures in the range of about 150
-450 F. The ratio of synthesis gas to olefin feed may vary widely ; in

7. general, about 2500 to 15, 000 cubic feet of HZ+CO per barrel of
olefin feed are em- ployez'.
At the end of the first stage, when the desired conversion of olefins
to oxygenated compounds has been effected, the product and unreacted
material are. generality withdrawn to a. catalyst removal zone where
dissolved catalyst is removed from the mixture by thermal treat- ment
in the presence of an inert gas, a vapor, hot water, or dilute acid.
Thereafter, the aldehydic reaction product is generally hydro genated
to the corresponding alcohol.
It has been recognized that substantially all forms of cobalt catalyze
this reaction, for the active catalytic agent is cobalt hydrocarbonyl
in all probability, this compound is synthe- sized in situ from the
cobalt compound or metal originally introduced. However, it has been
preferred to employ the compounds of cobalt that are oil-soluble, such
as high molecular weight salts of cobalt, i. e. cobalt oleate or
naphthenate. These materials form a homo- geneous reaction mixture and
have a high reactivity or reaction rate, substantially higher than
cobalt metal or oxide, or aqueous solutions of cobalt salts, such as
cobalt formate or acetate. However, the use of high molecular weight
cobalt carboxylates has certain disad- vantages. They are pensive to
prepare, requiring a variety of processing steps, and also contaminate
the final reaction product with the acid or ester corresponding to the
carboxylate employed. Furthermore, though the reactivity and reaction
rates are high, leading to high olefin conversions, the aldehyde and
alcohol selectivity resulting from use of these catalysts is not
always satisfactory, and may be somewhat low.
An alternativesystem is the use of metallic cobalt or slurry of cobalt
oxide. These catalytic agents, though they have no residues to
contaminate the aldehyde or alcohol product, and though they give a
better alcohol selecti- vity than the oil-soluble cobalt soap, have a
very slaw reaction rate. This is a very serions ; defect in continuous
operation, for low reaction rates mean low throughput rates.
Still another alternative has been the use of aqueous solutions of
water-soluble cobalt salts, such as cobalt acetate. Here also the
reaction rates of the aqueous solution are considerably slower at a
given temperature than those of oil-soluble cobalt salts. Furthermore,
in order to add an amount of cobalt acetate equivalent to cobalt
oleate to provide the desired cobalt concentration of about 0. 3
weight percent, about 5-6 volume % of water (based on olefin) must be
added to the olefin feed. Such a system has been found not to function
efficiently, and to give a more unfavourable feed rate for a given
olefin conversion relationship than cobalt oleate catalyst at
equivalent cobalt concentration. This is illustrated in the following
example, where a heptene fraction from a propylene-butylene

8. polymerization unit was continuously carbonylated with 0. 3 wt. % of
cobalt catalyst at 340-350 F.
Liquid Con
Feed Rate version
Catalyst System V/V/Hr. Mol %
Cobalt Oleate in Olefin 0. 6 80
Cobalt Oleate in Olefin 1. 2 74
Cobalt Acetate in Water 0. 6 72
Cobalt Acetate in Water 1. 2 54
Thus with the aqueous cobalt acetate catalyst it is necessary to
decrease olefin feed rate by almost 5OoO to achieve a conversion level
equivalent to cobalt oleate.
The relative reaction rates of a number of types of cobalt-containing
substances at a temperature of 340350 F. are listed below :
Induction Reaction
Period Rate
Catalyst Min. kx 102
Cobalt oleate 30 7. 8
Cobalt acetate solution
(4% water in olefin) 20 1. 4
Cobalt Carbonate, Solid 5 0. 5
Cobalt Oxalate, Solid 5 0. 5
Cobalt Formate,
Basic, Solid 5 0. 5
Cobalt Sulfat 7HOO < 5 0. 7 oba. lt Oxiv 4-5 0. 5
Cobalt Metal 4-7 0. 5
These Sgures show the great diversity in reaction rates characterizing
various cobalt catalyst systems. The low reaction rates of the cobalt
salts such as the oxalate, and carbonate and of Ithe oxide and metal
are a direct result of the low rate of conversion of these solids to
active catalyst, i. e. cobalt hydrocarbonyl.
The present invention comprises a process for reacting olennic
compounds with a mixture of H2 and CO in the presence of a cobalt
catalyst at elevated tein-oerotures and pressures in a reaction zone
to produce an aldehyde product, wherein the catalyst consists of an
oxide of cobalt promoted with an organic acid having from two to seven
carbon atoms per molecule.
It is found that such a catalyst provides a reaction rate of the same
magnitude as the oil soluble cobalt salts, for example, cobalt oleate
previously used but is much cheaper and not associated with the
disadvantages resuIting from the use of oil soluble salts.
The acid may be introduced into the reaction zone in any convenient
manner, either with the Oxo catalyst as a slurry, or separately as,
for example, admixed with the olefin feed or recycle stream. In a

9. preferred embodiment, cobalt oxide is employed as a slurry in an
organic liquid preferably the olefin feed, and glacial acetic acid is
admixed with the said slurry. The slurry may be injected into the
Oxo reactor by any conventional method of adding a slurry to a system
under pressure.
Such methods include slurry pumps, injectors and surge systems.
Alternatively the cobalt oxide may be slurried in an organic liquid or
part of the olefin feed and supplied to the reaction zone and the
remainder of the olefin feed and the acid fed to the reaction zone
separately or together. According to another form the cobalt oxide may
be in the reaction zone as a fixed bed and the necessary quantity of
acid fed to the reaction zone continuously together with or separately
from the olefin feed. One embodiment of a system suitable for carrying
out the present invention is shown diagram- matiaally in Figure I of
the accompanying drawings.
Turning now to Figure I, solid cobalt oxide of suitable
particlesizeisintroducedinto mixing chamber 2 through hopper 4.
Sufficient olefin feed or Oxo product is added to the mixing chamber
through line 3 to form the said cobalt oxide Snto a slurry containing
from 2 to 10% solids. Glacial acetic acid is then added to the extent
1-6 mols of acid per mol of cobalt oxide, preferably 3-4. 5 mols acid
per mol of oxide. By means of the circulation pump 6, the mixture of
cobalt oxide slurry and acid is circulated through lines 8, 10 and 15
to bo ! th the top and bottom of ! the mixing chamber. By means of a
suitable surge pump liquid olefin or Oxo product is-introduced through
lines 14 and 16 into surge vessel 18.
The system is so designed that except under positive action from the
surge pump, the pressure in the surge vessel is sufficiently low to
allow slurry te pass through the lower check valves 12. Under positive
action from the surge pump, theslurry is forced through the upper
check valves 20.
The slurry of cobalt oxide disperse in the acetic acid and olefnn feed
or other organic medium, such as recycle aldehyde product or even
alcohol distillation bottoms, is thus continuously injecte into
carbonylation reactor 24 through line 22. The slurry which consists of
about 0. 1 to 3% by weight of cobalt oxide calculated as cobalt, may
be injecte at the rate of about 5 to 200 pounds per barrel of olefin,
at pressures preferably equal to or slightly higher than those
prevailing in reactor 24.
A gas mixture comprising H2 and CO in approximately equal volumes,
though 0. 5-2 volumes lI2/CO may be used, is supplie through line 26
andHowsconcurrentlywith preheated liquid olefin feed admitted through
line 28, and with the catalyst slurry. Reactor 24 is preferably
operated at pressures of about 2500-3500 psig. and temperatures of

10. 300-375 F, depending upon the olefin feed and other reaction
conditions. Liquid feed rates of 0. 2 to 2. 0 V/V hour may be
employed.
Liquid oxygenated reaction products consisting mainly of aldehydes,
containing cobalt carbonyl in solution, as well as unreacted syn-
thesis gases, are withdrawn overhead through line 30 from high
pressure reactor 24 and thereafter freed from dissolved and suspended
cobalt. Thus, the cobalt contaminated aldehyde product may be freed of
dissolved cobalt by heating it in the presence of water or dilute
acid, in particular dilute acetic acid, and thereafter hydrogenatedto
the corresponding alcohol. If desired, it may be highly advan- tageous
to filter the Oxo reactor effluent prior to or subsequent to
decobalting, or both.
The process of the present invention may be further illustrated by the
following specific example.
EXAMPLE
The experimental procedure consisted in charging the olefin and solid
catalyst to a bomb at room temperature, bringing the bomb up ta 100
psig. with 1/1 synthesis gas and heating to the desired reaction
temperature, quickly increasing the synthesis gas pressure to 3000
psig., withdrawing samples of the product as the reaction proceeded
(400-500 psig. drop) and stopping the run when final pres- sure had
decreased to 1000 psig. The final olefin conversion was of the order
of 4555% in all cases. The product samples were inspected for soluble
cobalt content and olefin conversion, and the latter values used to
calculate the average reaction velocity constant "k." Feed #C7
Olefins#C12 Olefins#
Feed charge (including catalyst) #1067 grams (1500 c.c.)#
Catalyst (0.2% by wt. of Cobalt Cobalt Plus Cobaltous plus Cobalt
Cobalt Plus cobalt on feed) Oleate Oxide Acetic Oxide Acetic Oleate
Oxide Acetic
Acid Acid Acid
Grms. catalyst 21 2.99 2.99 2.7 2.7 21.0 2.99 2.99
Grms. acetic acid - - 2.30 - 2.3 - - 2.3
Temperature, F. 358 356 361 358 375 351 347 365
Pressure at Start, Psig. #3000#
Pressure at End, Psig. #1000# 3000 1000
% Olein Conversion 47.5 48.5 47 58 43 52 ( 49.5
Reaction Constant, k # 102 9.0 0.5 6.9 0.7 6.7 6.0 * 1.3
Relative Catalyst Activity 1 0.05 0.76 0.08 0.75 1 - 0.22 to Cobalt
Oleate
Inspection of Products #
% Soluble Cobalt 0.13 0.001 0.005 0.007 0.002 0.12 0.000 0.01
CO No. 183 173 183 153 58 65

11. OH No. 26 48 32 52 116 100
Saponification On. 9 7 21 17 22 12
Acid No. 0.3 1 3 3.4 4.2 2.1 * No reaction after 5 hours.
These results show clearly that while e cobaltic and cobaltous oxide
show low activity of 1/15-1/7 that of cobalt oleate catalyst, the
addition of 0. 1% by weight based on olefine feed of acetic acid to
the oxides results in a 10 fold increase in catalyst activity and
shorter induction period. A similar order of catalyst activity is
noted in both the oxonation of a C, and the more difficultly oxonat-
able 1r2 olefin.
The effect of the addition of acid to cobalt oxide catalyst is shown
clearly in figure 2 of the accompanying drawings, showing the
variations of the reaction velocity constant with the addition of
various adds, at various, mol ratios. These data show that organic
acids in general have some effect ; the most notable being shown by
acetic acid. Formic acid, on the other hand, actually was found to
inhibit the reaction. This is consonant with the general finding that
the first members of homologous series have characteristics different
from those of higher members.
It is also. noted that the highest rate increase effect is attained,
in the case of acetic acid, at about 3-4 mols of acid per mol cobalt
oxide used. The commercial cobalt oxide employed in these experiments
analyzed about 25 % CoO and 75 % of the double compound
CoO'-CoOg. This material is substantially completely insoluble in
glacial acetic acid and even with H2SO4 is digested with a great deal
of difficulty. On a stoichiometric basis, 6 mols of acetic acid would
be associated with one mol of the commercial oxide calculated as
cobalt acetate. The results, however, show that maximum increases in
rates are obtained at an acid/oxide ratio less than. this
stoichiometric quantity. These considerations would indicate that
cobalt acetate is probably not formed in the course of the reaction
or, if formed, it is present in an activated state.
Toi determine whether it is the extent of acidity or degree of
ionization that is res- ponsible for the increase in reaction rate,
further experiments were carried out at 325 F. and 3000 psig.
employing 85% phosphoric acid. No enhancement in activity of the
cobalt oxide was observed even iafter 3 hours. Formic acid also, as
has been pointed out, gave no enhancement. This add also is 10 times
stronger than acetic acid. Toluene sulfonic add, which is also
sstronger than acetic acid, gave some increase, but not to the extent
found with acetic acid.
Not all forms of cobalt may be activated in the manner described, but
apparently only oil-and water-insoluble forms, such as the cobalt
oxides. Thus figure 3 of the accompanying drawings clearly shows that

12. cobalt metal is unresponsive to the acid treatment, while solid cobalt
acetate actually decreased in neaction velocity.
The process of the present invention may be modified-in many ways
without departing
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* GB784630 (A)
Description: GB784630 (A) ? 1957-10-09
Organosiloxane emulsions
Description of GB784630 (A)
A high quality text as facsimile in your desired language may be available
amongst the following family members:
FR1171982 (A) NL94246 (C) US2755194 (A)
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The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
PATENT SPECIFICATION
784,630 Date of Application and filing Complete Specification Jan 19,
1956.
No 1860/56, Application made in United States of America on Feb 7,

13. 1955.
Complete Specification Published Oct 9, 1957.
Index at Acceptance:-Class 2 ( 7), T 6 (D 2: Dll: F 1: F 2: HI: J 1).
International Classification: -C 08 g.
COMPLETE SPECIFICATION
Organosiloxane Emulsions We, MIDLAND SILICONES LIMITED, a British
Company, of 19, Upper Brook Street, London, W.1, do hereby declare the
invention, for which we pray that a patent may be granted to us, and
the method by which it is to be performed, to be particularly
described in and by the following statement: -
This invention relates to novel organosiloxane emulsions.
Organosiloxane emulsions, especially oil-inwater type emulsions, have
been employed for a wide variety of uses such as car and furniture
polishes, release agents, medicinal preparations, and cosmetics The
unique properties of organosiloxanes and the ease with which
organosiloxane emulsions can be used have assured them of an expanding
popularity in industry.
One of the most important properties sought in an emulsion is
stability An emulsion can be defined as a dispersion of fine liquid
particles within another immiscible liquid Such dispersions have a
tendency to "break" or "cream " A very unstable dispersion, such as
benzene in water, will separate very rapidly and can hardly be called
an emulsion The very best emulsions exhibit practically no "creaming"
and are said to be stable.
There are many factors involved in the stability of emulsions and
among the important factors are the emulsifying agent or agents
employed, the particle size of the dispersed liquid, the nature of the
dispersed liquid and the continuous or dispersing liquid Many
experiments have been carried out and much has been written concerning
such factors with relation to organosiloxane-in-water emulsions.
In fact, relatively satisfactory siloxane emulsions have been
available heretofore but certain deficiencies are still present.
Heretofore, the organosiloxane-in-water emulsions have been largely
inconsistent in their behaviour One production batch would be very
stable, whereas the next batch might prove to have quite
unsatisfactory stability.
Unfortunately, the emulsions often" break" or cream after they have
been shipped to the ultilPrice 3 s 6 d l mate user (e g, a rubber
fabricator for use in rubber moulds) The consumer usually fails to
recognise that separation has occurred until 50 he finds that the
supposed emulsion is not accomplishing the desired result (e g, the
rubber sticks to the moulds rather than being freely released)
Therefore, it is of primary economic importance to the consumer and
the 55 producer of organosiloxane-in-water emulsions that a

14. consistently stable emulsion be found.
Separation or creaming in an emulsion can be the result of many
variables including repeated freezing and thawing of the emulsion, 60
protracted standing, and too large a particle size in the emulsion as
produced.
It is the primary object of this invention to prepare an
organosiloxane-in-water emulsion exhibiting a consistently
reproducible 65 degree of stability heretofore unavailable.
Another object is to produce an emulsion having a uniformly fine
particle size heretofore unobtainable A further object is to produce
an emulsion which will not separate or cream 70 after repeated
freezing and thawing A further object is to produce an
organosiloxane-inwater emulsion which remains stable on storage for
several months or years.
In accordance with this invention an organo 75 siloxane-in-water
emulsion consists essentially of (A) from 0 05 to 90 per cent by
weight calculated on the total emulsion of an organic solvent-soluble
organopolysiloxane having the average general formula RD Si O 4 _n
wherein 80 each R is a monovalent hydrocarbon radical or a halogenated
monovalent hydrocarbon radical and N has an average value of from 0 9
to 3 0, (B) from 3 to 45 per cent by weight calculated on the weight
of (A) of the trimethylnonyl ether of a polyethylene glycol, (C) 0 1
to 1 5 per cent by weight calculated on the weight of (A) of a sodium
salt of an alkylated aryl polyether sulphate, and (D) the balance of
the emulsion being water.
The organosiloxane lingredient (A) abovel can be any organosilicon
compound having the average general formula Rn Si OQ_, wherein each R
is a monovalent hydrocarbon radical or a halogenated monovalent
hydrocarbon radical.
Illustrative of the wide range of radicals R can represent are alkyl
radicals such as methyl, ethyl, butyl and octadecyl; alkenyl radicals
such as vinyl and allyl; aryl radicals such as phenyl, naphthyl and
xenyl; alicyclic radicals such as cyclohexenyl, cyclopentenyl and
cyclohexyl; alkaryl radicals such as tolyl and xylyl; and aralkyl
radicals such as benzyl, and/or any halogenated monovalent hydrocarbon
radical such as tetrafluoroethyl, perfluorovinyl, dichlorophenyl,
and,7,-trifluorotolyl.
The organosiloxanes which are operative herein range from resins
having an average of 0 9 organic radicals per silicon atom to liquids
having an average of 3 organic radicals per silicon atom It is
apparent to those skilled in the art that the siloxane must be a
liquid or must be soluble in an organic solvent in order to prepare an
emulsion therefrom Any siloxane having 2 or 3 organic radicals per
silicon atom can be characterised as a liquid although the viscosity

15. of such material can range from less than 10 cs at 25 C to more than
10,000,000 cs at 25 C The resinous siloxanes (i.e, degree of
substitution= 0 9 to 2) can be in the liquid state or can be solid or
gel-like and yet be operative herein so long as they can be dissolved
in an organic solvent such as toluene, benzene, naphtha and other
petroleum solvents Preferred are the organosiloxanes having 2 to 3
organic groups per silicon atom.
There are two emulsifying agents employed herein The trimethylnonyl
ether of a polyethylene glycol is employed in conjunction with a
sodium salt of an alkyl aryl polyether sulphate It has been found that
when these two agents are employed in the emulsions of this invention
in the amounts specified, significantly better emulsions are obtained
than could be prepared with either agent alone or in combination with
any other agent The particle size of the dispersed organosiloxane is
greatly reduced to 0 5 microns and smaller.
As a result of this outstanding and unexpected reduction in particle
size the dispersed particles are more uniform in size and are more
uniformly distributed throughout the emulsion system This in turn
results in increased heat stability, reduces the creaming to the point
of eliminating it, and allows easy dilution of the emulsion to any
desired useful concentration (e g, 0 05 per cent by weight of
organosiloxane).
From a practical, commercial standpoint, the emulsions of this
invention are extremely welcome to the producer and the consumer The
producer can be assured of uniform quality of product and good product
control This reduces costly returns of unsatisfactory material and
saves time and money heretofore spent in trying to obtain a
commercially saleable product from the unsatisfactory batches 65 of
emulsion.
The consumer is now assured of a noncreaming emulsion exhibiting
improved properties over those obtained with earlier commercial
emulsions Because of the uniformity 70 of the new emulsion, any
coating made with it will be more uniform in thickness and quality
Further, special handling techniques heretofore employed have been
largely eliminated with the emulsions of this invention 75 The
emulsions of this invention can be prepared in any desired manner The
preferred method is to add the trimethylnonyl ether of polyethylene
glycol and the sodium salt of alkyl aryl polyether sulphate to the
organo 80 siloxane, and intimately intermix them by milling or mixing
by any desired means This mixture is then added to water with
appropriate mixing techniques employed to secure a stable, uniform
emulsion Alternatively, all of 85 the ingredients can be admixed in a
single step by adding them together and mixing.
The amount of organosiloxane employed should be at least 0 05 per cent

16. by weight based on the total weight of the emulsion 90 Although this
invention is operative with less than 0 05 per cent of organosiloxane,
it is impractical to reduce the organosiloxane below this amount and
thus practically dilute out its effectiveness The upper limit on the
propor 95 tion of organosiloxane to water lies at the inversion point
of the emulsion, that is at the point where the
organosiloxane-in-water emulsion inverts to become a
water-in-organosiloxane emulsion This is generally at a point 100 of
about 90 per cent by weight of organosiloxane.
The emulsions of thisinvention are primarily useful as mould release
agents such as are employed by rubber fabricators, and plastics 105
fabricators They are also useful in emulsions employed to render
fabrics and/or leather water repellent Various uses of these materials
will require the addition of rust inhibitors, anti-oxidants and other
additives and this 110 invention is intended to include the addition
of minor amounts of such additives.
The following examples illustrate the invention All parts and
percentages in the examples are by weight unless otherwise specified
115 EXAMPLE 1.
parts of a liquid dimethylsiloxane having a viscosity of 350 cs at 25
C were added to 1.8 parts of trimethylnonyl ether of polyethylene
glycol, having a molecular weight of about 120 609, and containing 9
to 11 ethylene oxide radicals per molecule (available commercially as
Tertigol TMN) and 0 15 part of a sodium salt of alkyl aryl polyether
sulphate (available commercially as Triton W-30 the word 125 "Triton"
being a Registered Trade Mark).
This mixture was manually mixed using a 784,630 784,630 stirring rod 5
parts of water were added to the mixture and the entire mix was sent
through a colloid mill Thereafter 10 parts of water were added and the
mix again was sent through the colloid mill Finally 47 5 parts of
water were added with the mix again being sent through the colloid
mill The colloid mill was set at medium for the first milling
operation and was set progressively finer with each succeeding milling
until on the final milling it was set at the extremely fine position
The resulting emulsion had particles of 0 5 W or lower It was very
stable and did not cream after months on the shelf Centrifuging for 30
minutes at an average force of 1200 times the force of gravity
produced less than 2 per cent.
separation and the gentle shaking quickly rehomogenised the emulsion
The emulsion did not break or cream after extended heating and boiling
nor did repeated freezing and thawing result in separation or creaming
This emulsion was the equal of any heretofore known in all physical
properties and was far superior in heat stability, shelf life,
compatibility, ease of emulsifying and dilution, average particle

17. size, hard water stability and pumping stability.
EXAMPLE 2.
Employing the process of Example 1, an emulsion was prepared
containing 35 parts of a phenylmethylsiloxane copolymer consisting of
50 mol per cent phenylmethylsiloxane, 28 mol per cent of
monomethylsiloxane, 14 mol per cent of monophenylsiloxane, and 8 mol
per cent of diphenylsiloxane dissolved in 35 parts of xylene, 2 8
parts of the trimethylnonyl ether of polyethylene glycol of Example 1,
0 2 part of the sodium salt of alkyl aryl polyether sulphate of
Example 1 and 61 parts of water.
This emulsion was equivalent to that which was obtained in Example 1.
EXAMPLE 3.
Equivalent results, were obtained when a vinylmethylsiloxane or a
chlorophenylethylsiloxane was substituted for the dimethylsiloxane of
Example 1.
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* GB784631 (A)
Description: GB784631 (A) ? 1957-10-16
Improvements in or relating to road or like rollers
Description of GB784631 (A)
PATENT SPECIFICATION
72 A-,03 1 Date of filing Complete Specification: Jan 4, 1954.
Application Date: Jan 5, 1953.
No 245153.
Complete Specification Published: Oct 16, 1957.
Index at acceptance:-Class 144 ( 2), C 2 A.
International Classification:-B 62 g.

18. COMPLIETE SPECIFICATION
Improvements in or relating to Road or like Rollers We, EDDISON PLANT
LIMITED, a British Company, of Syston Lane, Belton, Grantham, and
ERNEST JOHN SPRIGGS, a British Subject, of the Company's address, do
hereby declare the invention, for which we pray that a patent may be
granted to us, and the method by which it is to be performed, to be
particularly described in and by the following statement: -
This invention relates to road, footpath and similar rollers and is
concerned with the provision of rubber or other resilient treads for
the roller wheels of such vehicles with the object of reducing the
road shocks, vibration and consequent wear and tear throughout the
machine which are experienced while such vehicles are travelling on
the highway, and also increasing road adhesion and improving
travelling speed.
According to the invention a resilient tread for a roller wheel of a
road or like roller comprises a plurality of pads of rubber or other
resilient material arcuate in the direction of their length and linked
together end to end to encircle the periphery of said roller wheel and
a flexible tensionable element which also encircles said periphery and
overlies said plurality of pads so that when tightened it secures said
plurality of pads in position, portions of the pads projecting
forwardly and rearwardly at the front and rear ends of each pad so
that they are disposed respectively in front of and behind
complementary portions of the adjacent pads as a result of which some
portion of the surface of the complete annular tread formed by the
linked pads is always in contact with the ground and thereby ensures a
smooth rolling action.
Preferably each of the pads comprises a substantially rectangular
cushion of rubber or other resilient material bonded or otherwise
secured to the convex surface of a substantially rectangular metal
base plate curved from end to end to conform substantially to the
curvature of the circumference of the roller wheel to which the pads
are to be attached The flexible element may comprise, for example, a
wire rope or cable which encircles a portion of the metal base 50
plates of the plurality of arcuate pads which is devoid of overlying
rubber or other resilient cushion.
Alternatively each of the pads may be composed wholly, or
substantially wholly, of 5 s rubber or other resilient material-that
is to say the cushion and base plate may be constructed in one piece
in rubber or other resilient material-the flexible element in this
case being in the form of a metal band 60 Preferably the said
plurality of arcuate pads are linked together by means of pin and slot
connections formed between the front and rear ends of adjacent pads
Two wire ropes or cables, or two metal bands, are ad 65 vantageously

19. employed which encircle lateral side portions of the substantially
rectangular metal or rubber or like base plates of the pads to which
lateral side portions the resilient cushion of such pads does 7 Q not
extend.
A preferred embodiment of the invention will now be described, by way
of example, with reference to the accompanying drawings in which: 75
Figure 1 is a plan view of one pad and a portion of an adjacent pad of
the resilient tread, Figure 2 is a broken side elevation of the pads
shown in Figure 1, 80 Figure 3 is a side elevation on a somewhat
larger scale of a toggle device for connecting the opposite ends of
one of the flexible elements and placing tension on the latter to
retain the pads in position, the figure show 85 ing the lever and link
of the toggle device straight, instead of being curved to conform to
the periphery of the roller wheel as in actual practice, to render the
pivotal arrangement of the toggle device more 90 readily
understandable, and Figure 4 is a plan view of the toggle device 2
784,631 shown in Figure 3.
Referring to Figures 1 and 2 of the drawings, a series of similar pads
10, each comprising a relatively thick cushion 1 of rubS her or other
resilient material of suitable composition and bonded or otherwise
secured to a relatively thin steel base plate 12, are linked together
to form a continuous tread for each of the roller wheels, front and
rear, of a road, footpath or similar roller.
Each pad formed by the aforesaid resilient cushion 11 on its steel
base plate 12 is a completely separate unit constituting one link of
the tread and the number of links required to form the tread of a
given roller wheel is governed by the circumference of the latter The
surface of each steel base plate 12, which is of generally rectangular
plan form, is curved from end to end, as shown in Figure 2, to conform
to the curvature of the circumference of the roller wheel to which it
is to be attached.
The lateral side portions 13 of each substantially rectangular steel
base plate 12 are left free of the overlying resilient cushion 11 and
at one end each of such lateral side portions is provided with an
upstanding headed pin 14 while at its other end it is formed with a
longitudinally extending lug 15 which is 310 joggled outwardly, as
shown at 515 a, relatively to the centre of curvature of the plate to
permit the lug to overlie the adjacent base plate An elongated slot 16
of slightly greater width than the diameter of the pins 14 is formed
centrally in each of the lugs and is enlarged at its outer end, as
shown at 16 a, to allow the head of one of the pins of the next pad to
pass through such enlarged portion In order to link the pads 10
together to form the complete annular tread the pins 14 are inserted
into the enlarged portions 16 a of the slots 16 at the adjacent ends

20. of adjacent pads after which the pads are slid towards each other in a
longitudinal direction to bring the head of each pin over the narrow
portion of the slot.
It will be appreciated that the movement of the pins 14 forwards or
backwards along the elongated slots 16 permits lengthening or
shortening of the complete tread, the maximum lengthening of the
latter being equal to the length of the narrow portion of each slot
minus the diameter of the pin, multiplied by the number of pads; the
length of each pad and the number of pads in each tread are so
determined that the maximum lengthening equals the length of one pad.
Although substantially rectangular in plan form the central portion of
each pad, i e the part of the base plate 12 having the overlying
resilient cushion 11 secured thereto, is formed with complementary
chevronshaped ends 17, 18 so that the rear end 18 of one pad has
portions disposed behind portions of the front end 17 of the following
pad in the line of travel whereby some portion of the surface of the
comilete annular tread formed by the linked pads is always in contact
with the ground, thus ensuring smooth rolling action 70 A pair of
steel wire ropes or cables 19, shown in broken lines in Figures 1 and
2, encircle the lateral side portions 13 of all the pads 10 on each
side of the complete annular tread and are tightened to strap the 75
pads to the periphery of the roller whee 121 in a manner to be
described T' e ropes 19 lie on the outer surface of the side portions
13 of the base plates and are positioned between the pins 14 and the
side walls of the 80 cushions 11.
The wire ropes or cables 19 are of predetermined length and to one end
of each rope a steel hook 20 is welded or otherwvise secured, a
further and more elongated form 85 of hook 21 being welded to the
opposite end of each rope as shown in Figures 4 and 5.
In order to secure and tighten the wire ropes 19 in position a toggle
device 22 is provided, comprising a lever 23 and link 24 pivotally 90
connected by a fulcrum pin 25 The lever 23 lies between the free ends
of the parallel limbs of the link 24, the opposite ends of such limbs
being connected by a pin 26 with which the hock 20 is engaged A
transversely 91 arranged pin 27 at the inner end of the lever 23 is
engaged with the hook 21 and when the free end of the lever is pressed
towards the surface of the side portion 13 of the base plate above
which the toggle 22 lies to bring 100 the lever and link 24 into
longitudinal alignment the two hooks 20 and 21 and the ends of the
rope 19 attached thereto are brought towards each other and are held
in tension to clamp and secure the pads 10 in position 105 Each limb
of the link 24 is provided with a series of equally spaced holes 28
with any opposite two of which the fulcrum pin 25 can be selectively
engaged to shorten or lengthen the toggle device 22 and thus obtain

21. 110 adjustment of the tension on the rope 19.
The transverse pin 27 is arranged on the longitudinal centre line of
the lever 23 and the holes formed in the latter to accept the fulcrum
pin 25 are arranged below such 115 centre line so that when the lever
is pressed downwardly to bring it into longitudinal alignment with the
link 24 the fulcrum pin is nearer the surface of the base plate 12
than the transverse pin 27 and the toggle de 120 vice 22 automatically
locks in position, the stem of the hook 21 being sufficiently thin to
allow the fulcrum pin to fall into position A hole 29 is, however,
provided on each side of the lever 23 through which a 125 locking pin
(not shown) can be inserted, such pin also engaging with an opposite
pair of the series of holes 28 in the limbs of the link 24 to finally
secure the toggle device in its locked position The series of holes 28
in 130 784,631 each ok the pads comprises a substantially rectangular
cushion and a base portion or 55 plate constructed wholly, or
substantially wholly, of rubber or other resilient material, the
cushion and 'base plate being constructed in one piece.
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* GB784632 (A)
Description: GB784632 (A) ? 1957-10-16
Improvements relating to glass lids
Description of GB784632 (A)
PATENT SPECIFICATION
Inventor: RALPH BROWN 78 d 4,132 Date of filing Complete
Specification: Sept 16, 1954.
Application Date: Sept 19, 1953.
Complete Specification Published: Oct 16, 1957.

22. Index at acceptance:-Class 66, A( 213: 6 A: 7 A 2: 7 A 5 B).
International Classification:-A 47 j.
COMPLETE SPECIFICATION
Improvements relating to Glass Lids We, THE B Ri W Is H HEAT RESISTING
GLASS COMPANY LIMITED, a British Company, of Phoenix Works, Loxdale
Street, Bilston, in the County of Stafford, do hereby declare the
invention, for which we pray that a patent may be granted to us, and
the method by which it is to be performed, to be particularly
described in and by the following statement: -
The present invention relates to moulded glass lids for dishes, and
has for its object to provide a new or improved construction which
will permit of ready removal of the lid from its associated dish when
so used or is alternatively will permit of its use when inverted as a
dish on its own account.
According to the present invention we provide a combination lid and
dish of moulded glass having a top wall and side walls extending
downwardly therefrom so as to form an inverted bowl or dish-like
member, the top wall having at its upper surface a portion or portions
constituting a base upon which the lid can stand in a stable manner
when inverted and also having a lifting handle which is accommodated
wholly in a recess in the top wall, the lower edges of the side walls
lying substantially below the lowest part of the under surface of the
top wall so as to render the lid suitable for use as a dish when
inverted.
In the foregoing statement and hereinafter the combination lid and
dish will be defined and described (except where the context
specifically otherwise requires) in its role as a lid and terms having
reference to a predetermined orientation (e g under surface and
upper-surface) are to be construed accordingly.
In a preferred form, the combination lid and dish of moulded glass is
formed as an inverted bowl or dish-like member having downwardly
extending side walls united to the periphery of a top wall having in
its upper surface a depression of which the lowest portion of the
under-surface does n Qt lPrice 3 s 6 d) project substantially below a
level half way down the inner-surfaces of the side walls, this
depression containing a handle of undercut form integrally united with
the bowl or 50 dish-like member, and having its upper extremity lying
below those portions of the upper-surface of the lid which surround
said depression and form a base upon which the lid can stand in a
stable manner when in i S verted for use as a dish.
For convenience in manufacture as well as to enhance the appearance it
is preferred that the depression has a part-spherical form or other
convenient concave form of curved 60 cross section.
The volumetric capacity of the article as a dish may be selected to

23. lie in the range one half to four pints.
From a more limited aspect a combina 65 tion lid and dish according to
the present invention comprises a pressed glass body formed as an
inverted bowl or dish-like member of approximately uniform wall
thickness having downwardly divergent side 70 walls and a top wall
including a depression of a depth not substantially greater than half
that of the side walls as presented at the under surface of the lid
and affording an under-surface which is free from pockets 75 grooves
or like local cavities difficult of access for cleaning purposes and
which merges with the inner-surfaces of the side walls, likewise free
from such cavities, through a rounded corner of sufficient radius 80
to avoid retention or entrapping of particles of food stuff, the
depression containing a handle of undercut form integrally united with
the top wall and formed therewith in the same pressing operation, such
handle 85 lying wholly beneath the rim of the depression.
The handle may comprise a pair of rib like handle elements extending
transversely of the recess or depression and undercut form 90 in cross
section, such handle elements being united integrally with the base
and/or sides No 25906/53.
of the recess or depression.
Each of these handle elements may have a web united integrally with
the base of the depression and a thickened flange or bead I at the
upper edge of such web and between adjacent ends of thle webs may be
left a gap which is overhung by inwardly projecting end portions of
the flanges or beads This latter feature enables the user to lift the
lid by meeting the first finger and thumb of one hand through the gap
and utilising the overhlanging portions of the flanges or beads to
lift the lid, thereby avoiding any substantial contact with the webs
of the handle elements which owing to their being integrally united
with the base of the depression may attain a somnewhat higher working
temperature than the flanges or beads.
In our prior Patent No 696,520 there is claimed a moulded glass lid on
which is formed a handle comprising upwardly projecting limbs joined
integrally at their lower ends to the lid and having free upper end
portions defining a gapped bridge spaced above the surface of the lid.
The invention is illustrated in the acconmpanying drawings
wherein:Figure 1 is a plan view of one construction of combination lid
and dish in accordance with the invention.
Figure 2 is a cross sectional view of the jcombination lid and dish
shown in its role as a lid serving as a closure member for a vessel
body as illustrated, and Figure 3 is a similar cross sectional view
showing the combination lid and dish in its role as a dish.
X nh combination lid and 'di's ray be rnoulded from any suitable ('-T
If glass but l 40 gass of the known bore-silicate type is prefered,

24. such glass having a relati-;ey low co-Icient of thermal e xpanslson
n'ai:tingm the arile to be suajntd, witilt _a'c to iheaing and cooling
involved' in normal cc'king operations in an oven.
The body of the article may be -orimed as a glass pressing preferably
o aopro_'_mately uniform wall thic kness as illustra td and may be of
any desired configuration as seen in plan, for example circular (as
illustrated), but oval or rectangular shapes in tie latter case with
rounded corners may be utiiised if desired.
The marginal portions of the body may project downwardly and also
diverge from each other to constitute side walls 10 and these side
walls are united integrally with a top wall which, in the construction
illustrated, is formed over substantially its whole area as a
depression 11.
It will be understood that this depression need not occupy the whole
area of the top wall although this form is preferred in that it
enables a sufficiently deep depression to be produced whilst
maintaining the various radii involved in its junction with the side
walls as well as lthe radius of curvature of the under-surface of the
depression itself to be maintained at a high value, thereby avoiding
the danger of retaining or entrap 70 ping particles of food stuffs
when the article is m use as a dish.
The depression may have a depth of about one-half the depth of the
side walls although depths in the range one-third to 75 two-thirds the
depths of the side walls may be utfiised, and preferably thile
depression itself is in the form of a part-spherical or other suitably
curved shell as shown The under-surface of the depression itself and O
the inler surface of ti e side walls are smooth and free urom pockets,
grooves or the like local cavities which would be difficult of access
for leaning purpozes and the undersurface of the depression 11 merges
smoothly 85 withl the inner surface of the side walls through rounded
comrners 12 having a substantial radius as shown.
The outer surfaces of the side walls may be formed with
circumferentially extending 90 s Ihallow grooves intersecting with
each other in apexes 13 merely to enhance the exterior appearance, and
at the lower extremity of the side walls a rebate 14 may be formed for
mating with the rim 15 of a vessel body 95 16,when the article is in
use as a lid It will be apparent that the volumetric capacity of the
vessel body differs from that of the lid in its role as a dish thereby
affording the user a choice of volumetric capacities 100 Within the
depression is contained a handle which may comprise a pair of handle
elements 17 of rib like form extending diametrically of the
depression.
As best seen in Figure 3 all of these handle 10 j eiemenis may be
formed with a web 18 which is united integrally with the upper surface

25. of e depression 11 and the upper edge of each web may have an integral
flange or bead 19 which is thicker than the web so as to pro 110 duce
an undercut cross section.
Tiee inner end portions 20 of the flanges or beads 19 may be continued
beyond the inner edges 21 of the webs so as to overhang ti P 7 gap 22
left between the inner edges of 115 the webs, these latter
conveniently being of part circular form so that the gap 22 is in the
form of a circular or approximately circular hole This form of handle
construction has the advantages already pointed out 120 For the best
advantage the circular portion of the gap 22 may have a diameter of
about -s of an inch and the narrower part of the gap which lies
between the portions 20 of the flanges or beads may be about 3 of an
125 inch.
The upper extremities of the handle elements lie beneath the rim 23 of
the depression so that when in use as a dish as seen in Figure 3 the
article will stand in a stable 130 a 784,632 uniform wall thickness
having downwardly divergent side walls and a top wall including a
depression of a depth il Ot substantally 6 d greater than half hat Oif
he side walls as presented at the unde'-surface of the lid and
alfording an under- ur ce Wilicil is iree from poc e-s grooveb or ii e
locai cavlies ciificult or access or cleaning purposes and which 6,5
merges with the inner-surfaces of the side walls, likewise free from
such cavities, through a rounded corner of sufficient radius to avoid
retention or entrapping of particles of food stuff, the depression
containing a 70 handle of undercut form integrally united with the top
wall and formed therewith in the same pressing operation, such handle
lying wholly beneath the rim of the depression 75 6 A combination lid
and dish according to any of the preceding claims formed as a pressing
of borosilicate glass having a thermal coefficient of expansion low
enough to permit the article to be subjected to the 80 heating and
cooling involved in normal cooking operations in an oven.
7 A combination lid and dish according to any of the preceding claims
wherein the handle comprises a pair of rib-like handle 85 elements
extending transversely of the recess or depression and of undercut
form in cross section, such handle elements being united integrally
with the base and/or sides of the recess or depression 90 O A
combinsation lid and dish according
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